Copolymers of fluorinated polydienes and sulfonated polystyrene

ABSTRACT

Copolymers of fluorinated polydienes and sulfonated polystyrene and their use in fuel cell membranes, batteries, breathable chemical-biological protective materials, and templates for sol-gel polymerization.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is based on and claims priority to U.S. ProvisionalPatent Application Ser. No. 60/554,461, filed Mar. 19, 2004, which isincorporated herein by reference in its entirety.

GOVERNMENT INTEREST

The work was supported by the U.S. Department of Energy, EERE Program,through Oak Ridge National Laboratory, and by the U.S. Army ResearchOffice. The U.S. government has certain rights in the invention.

TECHNICAL FIELD

Copolymers of fluorinated polydienes and sulfonated polystyrene andtheir use in electrochemical cell membranes, for example, in fuel cells,as polyelectrolytes in electrochemical cells, such as batteries,fabrics, for example for use in breathable chemical-biologicalprotective materials, and templates for sol-gel polymerization, asrepresentative applications.

ABBREVIATIONS BHT = butylated hydroxy toluene BR = butyl rubber ° C. =degrees Celsius CO = carbon monoxide DABCO =1,4-diazabicyclo[2.2.2]octane DDQ =2,3-dichloro-5,6-dicyano-1,4-benzoquinone DLI = difunctional lithiuminitiator FPB = fluorinated 1,4-polybutadiene FTIR = Fourier transforminfrared GPC = gel permeation chromatography HFPO = hexafluoropropyleneoxide IR = infrared MALDI-TOF-MS = matrix assisted laser desorptionionization time-of-flight mass spectrometry MALLS = multiangle laserlight scattering Me = methyl NMR = nuclear magnetic resonance PαMS =poly(α-methylstyrene) PBD = polybutadiene PCHD = polycyclohexadiene PDI= polydispersity index PEM = proton exchange membrane PI = polyisoprenePS = polystyrene PSS = poly(styrene sulfonic acid) SABrE = selfassembling barrier elastomer SAXS = small angle X-ray scattering SANS =small angle neutron scattering SEC = size exclusion chromatography SEM =scanning electron microscopy TEM = transmission electron microscope TEP= triethylphosphate TGA = thermogravimetric analysis T_(g) = glasstransition temperature T_(m) = melting point

BACKGROUND

Robust, highly conductive, and inexpensive proton exchange membranes(PEMS) are needed for practical and reliable electrochemical cell, e.g.,fuel cell, operation at elevated temperatures. Current fuel cellmembranes typically are based on polymeric materials, such as thoseavailable under the registered trademark NAFION® from E. I. duPont deNemours and Co., Wilmington, Del., United States of America. A NAFION®polymer is a perfluorinated polymer comprising low levels of ionicgroups, which aggregate to form ionic, hydrophilic clusters. Thesehydrophilic clusters allow transport of water and ions across membranesformed from NAFION® polymer, making it a useful material for fuel cellmembranes, catalysis, and templating.

PEMs based on NAFION® polymers have long been considered benchmarks interms of performance characteristics. See Heitner-Wirquin, C., J.Membrane Sci. 120, 1-33 (1996). Fuel cell membranes based on NAFION®polymer suffer several disadvantages, however. For example, NAFION®polymer is expensive and typically cannot be used in applicationsrequiring temperatures in excess of 100° C. Also, the structure ofNAFION® polymer is complex and not fully understood.

Further, the current class of PEM fuel cells, which typically operate atabout 90° C., is hampered by sensitivities to carbon monoxide (CO) andperoxide formation that limit performance and require the use of highpurity fuels. To overcome such sensitivities to CO, complex systems arerequired to remove CO from the fuel. Further, platinum catalyststypically are required on the anode to minimize the effect of CO onmembrane polarization. A polymeric membrane capable of operating atelevated temperatures (e.g., temperatures above about 150° C.) wouldlargely eliminate such concerns, because CO adsorption is no longerkinetically favorable at those temperatures.

Given the importance of practical operations of fuel cells with highperformance, low cost, and extended lifetimes, various approaches to thesynthesis and characterization of PEM materials have been reported.Doyle et al., J. Electrochem. Soc. 147, 34-37 (2001), have reviewed anumber of alternative PEM systems, including polymer systems doped withacids or ionic liquids. Inorganic dopants and hybridization proceduresalso have been used in an effort to improve mechanical, thermal, andwater sorption properties of NAFION®-based PEMs. See Deng. Q., et al.,J. Appl. Polymer Sci. 68, 747-763 (1998); Antonucci, P. L., et al.,Solid State Ionics 125, 431-437 (1999).

There exists, however, a need in the art for improved materials forPEMs, in particular PEMs for sustained operation in fuel cells atelevated temperatures (e.g., temperatures above about 150° C.).

Further, there exists a need in the art for improved fabrics, forexample for use in breathable chemical and biological protectiveclothing for military personnel, emergency response teams, industrialand/or agricultural workers and other applications, and healthcareprofessionals. Standard protective clothing is made largely from butylrubber (BR), a material whose impermeability provides an excellent levelof protection, but also traps heat and moisture inside the garments. BRgarments also are bulky and limit dexterity. For example, a particularproblem with gloves made from BR materials is that they constrain handmovement. In a desert combat environment these problems could result inmore than simple discomfort and inconvenience.

Thus, there is a need in the art for improved materials for use as fuelcell membranes and as a fabric, for example for use in breathablechemical-biological protective clothing.

SUMMARY

In some embodiments, the presently disclosed subject matter provides amethod for forming a copolymer comprising a fluorinated polydiene and asulfonated polystyrene, the method comprising:

-   -   (a) providing a copolymer comprising a polydiene component and a        polystyrene component;    -   (b) reacting the polydiene component of the copolymer with a        fluorinating agent to form a fluorinated polydiene component;        and    -   (c) reacting the polystyrene component of the copolymer with a        sulfonating agent to form a sulfonated polystyrene component;        thereby forming a copolymer comprising a fluorinated polydiene        and a sulfonated polystyrene. In some embodiments, the presently        disclosed subject matter provides a copolymer comprising a        fluorinated polydiene and a sulfonated polystyrene.

In some embodiments, the copolymer comprising a fluorinated polydieneand a sulfonated polystyrene comprises an architecture selected from thegroup consisting of a diblock copolymer, a triblock copolymer, astatistical copolymer, a graft copolymer, and a miktoarm star copolymer.

In some embodiments, the polydiene component is selected from the groupconsisting of 1,4-polybutadiene, poly(1,3-cyclohexadiene), andpolyisoprene. In some embodiments, the fluorinating agent comprisesdifluorocarbene. In some embodiments, the polystyrene is selected fromthe group consisting of polystyrene and poly(α-methylstyrene). In someembodiments, the sulfonating agent is selected from the group consistingof acetyl sulfate and sulfur trioxide.

In some embodiments, the copolymer comprising a fluorinated polydieneand a sulfonated polystyrene comprises an AB block copolymer, whereinthe A block comprises a polystyrene and the B block comprises apolydiene. In some embodiments, the copolymer comprising a fluorinatedpolydiene and a sulfonated polystyrene comprises an ABA triblockcopolymer, wherein the A block of the triblock copolymer comprises apolydiene and the B block of the triblock copolymer comprises apolystyrene. In some embodiments, the copolymer comprising a fluorinatedpolydiene and a sulfonated polystyrene comprises a statistical copolymercomprising 1,3-cyclohexadiene and α-methylstyrene. In some embodiments,the copolymer comprising a fluorinated polydiene and a sulfonatedpolystyrene comprises a graft copolymer. In some embodiments, the graftcopolymer comprises an architecture selected from the group consistingof a trifunctional comb architecture, a tetrafunctional centipedearchitecture, a hexafunctional barbwire architecture, and a miktoarmstar architecture.

In some embodiments, the fluorinated polydiene is present in a greaterstoichiometric amount than the sulfonated polystyrene. In someembodiments, the method comprises optimizing an amount of thefluorinated polydiene, an amount of the sulfonated polystyrene, or anamount of both the fluorinated polydiene and the sulfonated polystyreneto provide a copolymer having a predetermined characteristic. In someembodiments, the predetermined characteristic is selected from the groupconsisting of hydrophilicity, permeability to water, thermal stabilityabove about 100° C., high glass transition temperature, high tensilestrength, elasticity, and chemical stability.

In some embodiments, the presently disclosed subject matter provides aproton exchange membrane comprising a copolymer comprising a fluorinatedpolydiene and a sulfonated polystyrene. In some embodiments, thepresently disclosed subject matter provides an electrochemical cellcomprising such a proton exchange membrane. In some embodiments, theelectrochemical cell comprises a fuel cell.

In some embodiments, the presently disclosed subject matter provides afabric comprising a copolymer comprising a fluorinated polydiene and asulfonated polystyrene. In some embodiments, the fabric comprises anarticle of chemical-biological protective clothing. In some embodiments,the fabric comprises an article of material used to cover anagricultural product.

In some embodiments, the presently disclosed subject matter provides atemplate for sol-gel polymerization comprising a copolymer comprising afluorinated polydiene and a sulfonated polystyrene.

In some embodiments, the presently disclosed subject matter provides amethod for preparing a sulfonated crosslinked poly(cyclohexadiene)polyelectrolyte, the method comprising:

-   -   (a) providing a poly(cyclohexadiene);    -   (b) crosslinking the poly(cyclohexadiene) to form a crosslinked        poly(cyclohexadiene);    -   (c) aromatizing the crosslinked poly(cyclohexadiene) to form a        poly(phenylene); and    -   (d) sulfonating the poly(phenylene) to form a sulfonated        crosslinked poly(cyclohexadiene) polyelectrolyte.

In some embodiments, the crosslinking comprises a polydienevulcanization process. In some embodiments, the aromatizing comprises adehydrogenation process. In some embodiments, the presently disclosedsubject matter provides a proton exchange membrane comprising across-linked poly(cyclohexadiene) polymer. In some embodiments, thepresently disclosed subject matter provides a polyelectrolyte comprisinga cross-linked poly(cyclohexadiene) polymer. In some embodiments, thecross-linked poly(cyclohexadiene) polymer is aromatized. In someembodiments, the cross-linked poly(cyclohexadiene) polymer issulfonated. In some embodiments, the cross-linked poly(cyclohexadiene)polymer comprises poly(1,3-cyclohexadiene).

Thus, in some embodiments, the presently disclosed subject matterprovides block graft copolymers with fluorinated blocks, as well ascharged blocks, for example, sulfonated blocks. If the content ofsulfonated polystyrene in the copolymer is relatively low, a structurehaving a hydrophobic semicrystalline continuous phase comprisingdispersed nanoscale ionic clusters will be generated via self-assembly.By regulating the composition, molecular weight, and architecture, thestructure, and thus the properties, can be optimized for a range ofapplications.

The presently disclosed fluorinated and sulfonated block copolymersprovide basic understanding in the synthesis, structure, and propertiesof new classes of materials useful in a range of applications includingportable power supplies, such as fuel cells and/or improved batteries,and protection against chemical and biological threats. The chemicalproperties of the materials provide an economical alternative for fuelcell membranes, while additionally allowing tailoring of relevantmechanical and transport properties through control of moleculararchitecture and chemical functionality.

Accordingly, it is an object of the presently disclosed subject matterto provide a new class of materials for use as a proton exchangemembrane. Further, it is an object of the presently disclosed subjectmatter to provide a new class of fabrics, such as materials that provideprotection against chemical and biological threats. These and otherobjects are achieved in whole or in part by the presently disclosedsubject matter.

Objects and aspects of the presently disclosed subject matter havingbeen stated hereinabove, other objects and aspects will become evidentas the description proceeds when taken in connection with theaccompanying Drawings and Examples as best described herein below.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1E are schematic representations of the presently disclosedbranched block copolymer architectures.

FIG. 2 is a photograph of a presently disclosed cross-linkedpoly(1,3-cyclohexadiene) (PCHD) membrane.

FIG. 3 is a miktoarm star morphology diagram based on experimentalresults.

FIG. 4 is a schematic of an electrochemical cell, such as a fuel cell,comprising a proton exchange membrane comprising the presently disclosedcopolymers of fluorinated polydiene and sulfonated polystyrene and thepresently disclosed cross-linked poly(1,3-cyclohexadiene) polymers.

FIG. 5 is a plot of the weight percent versus temperature for apresently disclosed cross-linked poly(1,3-cyclohexadiene) (PCHD)membrane. Line A represents the thermal analysis of a cross-linked PCHDmembrane. Line B represents the thermal analysis of a cross-linked PCHDmembrane after aromatization. Line C represents the thermal analysis ofa cross-linked PCHD membrane after aromatization and sulfonation.

FIGS. 6A and 6B are representative Fourier transform infrared (FTIR)spectra of a presently disclosed cross-linked poly(1,3-cyclohexadiene)(PCHD) membrane. FIG. 6A is an FTIR spectrum of a presently disclosedPCHD membrane. FIG. 6B is an FTIR spectrum of a presently disclosedsulfonated, aromatized PCHD membrane.

FIGS. 7A and 7B are representative scanning electron microscopy (SEM)micrographs of a presently disclosed cross-linkedpoly(1,3-cyclohexadiene) (PCHD) membrane. FIG. 7A is an SEM micrographof a presently disclosed PCHD membrane before sulfonation. FIG. 7B is anSEM micrograph of a presently disclosed PCHD membrane after sulfonation.

FIG. 8 is a diagram showing O₂ permeability as a function of morphologyand volume fraction.

FIGS. 9A and 9B are schematic diagrams illustrating transport paths insmall vs. large grain morphologies.

FIG. 10 is a graphical representation of gas permeability inpolystyrene-polydiene block copolymers vs. φ_(c)/T, wherein φ_(c) is thevolume fraction of the conductive microphase and T is the tortuosity oftransport paths in the conductive domains, wherein (♦) corresponds tothe Argon (Ar) permeability (▪); corresponds to the carbon dioxide (CO₂)permeability; and (▴) corresponds to the oxygen (O₂) permeability.

FIG. 11 is a graphical representation of stress vs. strain tensilecurves for hexafunctional polystyrene-polyisoprene graft polymers with21-vol % polystyrene and 2.7-, 3.6-, and 5.2-average number of branchpoints per molecule.

FIG. 12 is a graphical representation of tensile strength as a functionof the number of branch points in a polystyrene-polyisoprene graftcopolymer with tetrafunctional grafting and a polystyrene volumefraction of 0.22.

FIG. 13 is a schematic representation of microphase separation in amultigraft copolymer with tetrafunctional branch points.

FIG. 14 is a graphical representation of tensile strength as a functionof graft point functionality for samples with 22-vol % polystyrene andan average of four graft points per molecule.

DETAILED DESCRIPTION

The presently disclosed subject matter will now be described more fullyhereinafter with reference to the accompanying Examples and Drawings, inwhich representative embodiments are shown. The presently disclosedsubject matter can, however, be embodied in different forms and shouldnot be construed as limited to the embodiments set forth herein. Rather,these embodiments are provided so that this disclosure will be thoroughand complete, and will fully convey the scope of the embodiments tothose skilled in the art.

Unless otherwise defined, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this presently described subject matter belongs. Allpublications, patent applications, patents, and other referencesmentioned herein are incorporated by reference in their entirety.

Throughout the specification and claims, a given chemical formula orname shall encompass all optical and stereoisomers, as well as racemicmixtures where such isomers and mixtures exist.

The presently disclosed subject matter provides in some embodiments (1)synthesis of new fluorinated and charged block copolymers; (2)morphological characterization of these materials both in the bulk formand in the presence of water and salts; and (3) investigation ofapplication relevant material properties, such as mechanical properties,charge transport, and water transport.

As provided herein below, in some embodiments, anionic polymerizationcoupled with appropriate postpolymerization chemistry is used to createa wide range of charge neutral copolymers of various compositions andmorphologies.

I. Definitions

As used herein, the term “anionic polymerization” refers to an ionicpolymerization in which the kinetic chain carriers are anions.Accordingly, an anionic polymerization reaction is a chain reaction inwhich the growth of the polymer chain proceeds by reaction(s) between amonomer(s) and a reactive site(s) on the polymer chain with regenerationof the reactive site(s) at the end of each growth step. Anionicpolymerization typically takes place with monomers comprisingelectron-withdrawing groups, such as nitrile, carboxyl, phenyl, andvinyl, or with monomers that can stabilize the anions through resonance.These polymerizations are initiated by nucleophilic addition to thedouble bond of the monomer, wherein the initiator comprises an anion,such as hydroxide, alkoxides, cyanide, or a carbanion. In someembodiments, the carbanion is generated from an organometallic species,such as an alkyl lithium, e.g., butyl lithium, or a Grignard reagent.Anionic polymerization typically is used to produce macromolecules frommonomers that contain a carbon-carbon double bond, such as styreneand/or butadiene. Such reactions are referred to as anionic vinylpolymerization.

As used herein, a “monomer” refers to a molecule that can undergopolymerization, thereby contributing constitutional units, i.e., an atomor group of atoms, to the essential structure of a macromolecule.

As used herein, a “macromolecule” refers to a molecule of high relativemolecular mass, the structure of which comprises the multiple repetitionof units derived from molecules of low relative molecular mass, e.g.,monomers and/or oligomers.

An “oligomer” refers to a molecule of intermediate relative molecularmass, the structure of which comprises a small plurality of unitsderived from molecules of lower relative molecular mass.

A “polymer” refers to a substance composed of macromolecules.

A “copolymer” refers to a polymer derived from more than one species ofmonomer.

As used herein, a “block macromolecule” refers to a macromolecule thatcomprises blocks in a linear sequence. A “block” refers to a portion ofa macromolecule that has at least one feature that is not present in theadjacent portions of the macromolecule. A “block copolymer” refers to acopolymer in which adjacent blocks are constitutionally different, i.e.,each of these blocks comprises constitutional units derived fromdifferent characteristic species of monomer or with differentcomposition or sequence distribution of constitutional units.

For example, a diblock copolymer of polybutadiene and polystyrene isreferred to as polybutadiene-block-polystyrene. Such a copolymer isreferred to generically as an “AB block copolymer.” Likewise, a triblockcopolymer can be represented as “ABA.” Other types of block polymersexist, such as multiblock copolymers of the (AB)_(n) type, ABC blockpolymers comprising three different blocks, and star block polymers,which have a central point with three or more arms, each of which is inthe form of a block copolymer, usually of the AB type.

As used herein, a “graft macromolecule” refers to a macromoleculecomprising one or more species of block connected to the main chain asside chains, wherein the side chains comprise constitutional orconfigurational features that differ from those in the main chain.

A “branch point” refers to a point on a chain at which a branch isattached. A “branch,” also referred to as a “side chain” or “pendantchain,” is an oligomeric or polymeric offshoot from a macromoleculechain. An oligomeric branch can be termed a “short chain branch,”whereas a polymeric branch can be termed a “long chain branch.”

A “chain” refers to the whole or part of a macromolecule, an oligomer,or a block comprising a linear or branched sequence of constitutionalunits between two boundary constitutional units, wherein the twoboundary constitutional units can comprise an end group, a branch point,or combinations thereof.

A “linear chain” refers to a chain with no branch points intermediatebetween the boundary units.

A “branched chain” refers to a chain with at least one branch pointintermediate between the boundary units.

A “main chain” or “backbone” refers to a linear chain from which allother chains are regarded as being pendant.

A “long chain” refers to a chain of high relative molecular mass.

A “short chain” refers to a chain of low relative molecular mass.

An “end group” refers to a constitutional unit that comprises theextremity of a macromolecule or oligomer and, by definition, is attachedto only one constitutional unit of a macromolecule or oligomer.

A “comb macromolecule” refers to a macromolecule comprising a main chainwith multiple trifunctional branch points from each of which a linearside chain emanates.

A “statistical copolymer” refers to a copolymer comprisingmacromolecules in which the sequential distribution of the monomericunits obeys known statistical laws, including, but not limited toMarkovian statistics.

A “polyelectrolyte molecule” refers to a macromolecule in which asubstantial portion of the constitutional units has ionizable or ionicgroups, or both.

An “ionomer molecule” refers to a macromolecule in which a small butsignificant proportion of the constitutional units have ionizable orionic groups, or both.

A “star polymer” refers to a polymer comprising a macromoleculecomprising a single branch point from which a plurality of linear chains(or arms) emanate. A star polymer or macromolecule with “n” linearchains emanating from the branch point is referred to as an “n-starpolymer.” If the linear chains of a star polymer are identical withrespect to constitution and degree of polymerization, the macromoleculeis referred to as a “regular star macromolecule.” If different arms of astar polymer comprise different monomeric units, the macromolecule isreferred to as a “variegated star polymer.”

A “miktoarm star polymer” refers to a star polymer comprising chemicallydifferent (i.e., “mixed”) arms, thereby producing a star polymer havingthe characteristic of chemical asymmetry.

As used herein, the term “chemical-biological” refers to chemical and/orbiological agents, including hazardous and/or toxic chemicals andmicroorganisms, such as, but not limited to, chemical-biological warfareagents, viruses, bacteria, blood-borne pathogens, air-borne pathogens,industrial chemicals, and agricultural chemicals, in liquid, vapor, andaerosol forms.

As used herein, the term “breathable fabric,” “breathable material,” oran article, for example, an article of clothing, comprising breathablefabric and/or breathable material refers to a fabric and/or a materialthat allows perspiration products to escape from, for example, a body,while preventing the penetration and/or transport of undesired hazardousmaterials, such as, but not limited to, chemical-biological warfareagents, viruses, bacteria, blood-borne pathogens, air-borne pathogens,industrial chemicals, and agricultural chemicals, in liquid, vapor, andaerosol forms, through the fabric and/or material.

As used herein the term “alkyl” refers to C₁₋₂₀ inclusive, linear (i.e.,“straight-chain”), branched, or cyclic, saturated or at least partiallyand in some cases fully unsaturated (i.e., alkenyl and alkynyl)hydrocarbon chains, including for example, methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, octyl, ethenyl,propenyl, butenyl, pentenyl, hexenyl, octenyl, butadienyl, propynyl,butynyl, pentynyl, hexynyl, heptynyl, and allenyl groups. “Branched”refers to an alkyl group in which a lower alkyl group, such as methyl,ethyl or propyl, is attached to a linear alkyl chain. “Lower alkyl”refers to an alkyl group having 1 to about 8 carbon atoms (i.e., a C₁₋₈alkyl), e.g., 1, 2, 3, 4, 5, 6, 7, or 8 carbon atoms. “Higher alkyl”refers to an alkyl group having about 10 to about 20 carbon atoms, e.g.,10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. In certainembodiments, “alkyl” refers, in particular, to C₁₋₈ straight-chainalkyls. In other embodiments, “alkyl” refers, in particular, to C₁₋₈branched-chain alkyls.

Alkyl groups can optionally be substituted with one or more alkyl groupsubstituents, which can be the same or different. The term “alkyl groupsubstituent” includes but is not limited to alkyl, halo, arylamino,acyl, hydroxyl, aryloxyl, alkoxyl, alkylthio, arylthio, aralkyloxyl,aralkylthio, carboxyl, alkoxycarbonyl, oxo, and cycloalkyl. There can beoptionally inserted along the alkyl chain one or more oxygen, sulfur orsubstituted or unsubstituted nitrogen atoms, wherein the nitrogensubstituent is hydrogen, lower alkyl (also referred to herein as“alkylaminoalkyl”), or aryl.

As used herein, the terms “substituted alkyl,” “substituted cycloalkyl,”“substituted alkylene,” “substituted aryl,” and “substituted arylene”include alkyl, alkylene, and aryl groups, as defined herein, in whichone or more of the hydrogen atoms of the alkyl, alkylene, aryl orarylene group are replaced with another atom or functional group,including for example, halogen, aryl, alkyl, alkoxyl, hydroxyl, nitro,amino, alkylamino, dialkylamino, sulfate, and mercapto.

“Alkoxyl” or “alkoxyalkyl” refer to an alkyl-O— group wherein alkyl isas previously described. The term “alkoxyl” as used herein can refer toC₁₋₂₀ inclusive, linear, branched, or cyclic, saturated or unsaturatedoxo-hydrocarbon chains, including, for example, methoxyl, ethoxyl,propoxyl, isopropoxyl, butoxyl, t-butoxyl, and pentoxyl.

II. Synthesis of Fluorinated Polydiene and Sulfonated Polystyrene BlockCopolymers

The presently disclosed subject matter provides the synthesis,properties, and morphology of a range of polymers comprising partiallyfluorinated polydienes, such as 1,4-polybutadiene, isoprene andcyclohexadiene, and partially or fully sulfonated polystyrene.

Fluorination of polydienes by generation of difluorocarbene has beenreported by Cais, R. B., et al., Macromolecules, 19, 595 (1986), usingPhHgCF₃ as the fluorine source, and by Thomson, M. W., Macromolecules,22, 481 (1989), via irradiation of chlorofluorocarbons. Further, Ren,Y., et al., J. Am. Chem. Soc., 120, 6830 (1998), have reported a facilemethod for fluorination of polydienes based upon difluorocarbeneaddition. This reaction employs the relatively inexpensivehexafluoropropylene oxide as a reagent and does not lead to substantialchain scission or crosslinking.

For example, when polybutadiene with a high 1,4-microstructure istreated with hexafluoropropylene oxide, the conversion is quantitativeand the resulting semicrystalline polymer has a T_(g) of 89° C., a T_(m)of 150° C., and exhibits good thermal stability. A sample of similarlyfluorinated polyisoprene retained 99.7% of its weight when heated at200° C. under nitrogen for one hour. See Ren, Y., et al., J. Am. Chem.Soc., 120, 6830 (1998). Analogous chemistries carried out on1,4-polyisoprene, as well as polycyclohexadiene, yield an amorphousproduct, which also is of interest.

Copolymers of butadiene and styrene can be produced with a range ofarchitectures encompassing diblock, triblock, statistical, and graftcopolymers. Triblock copolymers of styrene and butadiene make up acommercially important class of thermoplastic elastomers. When anionicpolymerization is employed in the synthesis, well-defined structureshaving controlled molecular weights, compositions, and narrowpolydispersities can be synthesized.

In some embodiments of the presently disclosed subject matter, thesynthesis of block and graft copolymers of fluorinated polydienes (e.g.,butadiene, isoprene, and cyclohexadiene) and polystyrene sulfonateoccurs in three steps: (1) synthesis of the polystyrene (PS)-polydieneblock copolymer comprising the desired architecture and composition, (2)fluorination of the polydiene blocks, and (3) sulfonation of the PSblocks to yield the final product. The first two steps can yield twoother block copolymer materials, a conventional PS-polydiene, as well asa fluorinated polydiene-PS material.

In some embodiments of the presently disclosed subject matter, thepolybutadiene block of such materials can be partially fluorinated byreaction with difluorocarbene (or perfluoroalkyl iodides—see Scheme 1below), followed by sulfonation of the polystyrene blocks. Afterfluorination of the polybutadiene component, the polystyrene segmentscan be sulfonated using reagents, such as acetyl sulfate or sulfurtrioxide, to form poly(styrene sulfonic acid) (PSS).

Poly(styrene sulfonic acid) (PSS) is an effective proton conductor. Insome embodiments of the presently disclosed subject matter, if thecomposition of the copolymer is chosen so that the fluorinatedpolybutadiene (FPB) volume fraction is considerably larger than the PSSvolume fraction, i.e., the content of sulfonated polystyrene in thecopolymer is relatively low, then a structure having a hydrophobicsemi-crystalline continuous phase containing dispersed nanoscale ionicchannels is obtained via self-assembly. By tuning the composition,molecular weight, and architecture (readily done using anionicpolymerization), the morphology, structure, and properties ismanipulated.

Less pronounced hydrophobic/hydrophilic phase separation, which would bepresent in an FPB/PSS copolymer as compared to NAFION® material, canlead to advantages in methanol fuel cells due to their difference inpermeability. While these native FPB/PSS copolymer materials might lackadequate thermal stability for use in methanol fuel cells well above100° C., they can be provided at low cost. Also, subsequent modificationto form inorganic hybrid materials can be used to improve theirhigh-temperature capability.

Within the context of fuel cells, less distinct phase separatedmorphologies are beneficial in the sense of less-tortuous proton hoppingpathways. The process of fluorination, as described herein below,increases chemical stability. With regard to thermal and morphologicalstability, insertion of inorganic oxide nanostructures into the hardblock regions lock in the phase-separated morphology at temperaturesaround or exceeding 100° C. in the case of membranes expected to operateat high temperatures. Further, by tailoring gradients of intimatelyincorporated inorganic oxide nanostructures, water activity gradientsare generated for the purpose of water management optimization.

III. ABA Triblock Copolymer Cylinders

Triblock copolymers of styrene and butadiene make up a commerciallyimportant class of thermoplastic elastomers. The polybutadiene (PBD)block of such materials can be partially fluorinated by reaction withdifluorocarbene, followed by sulfonation of the polystyrene blocks.

A series of ABA triblock copolymers are synthesized, in which the outerA blocks are polydiene, e.g., isoprene (IS), polybutadiene (PBD), andcyclohexadiene (CHD), and the inner B block is polystyrene (PS). Thisarrangement is the opposite block arrangement to the normalthermoplastic elastomer KRATON®-like materials (KRATON Polymers U.S.LLC, Houston, Tex., United States of America) in which the PS blocks arein the A position on the ends of the molecule to provide mechanicalreinforcement. In some embodiments, the PS blocks are sulfonated. Insome embodiments, the PS blocks are hydrated. In embodiments wherein thePS blocks are hydrated, the PS blocks can be plasticized in the end-useapplication.

Once fluorinated, the polydiene blocks become strongly hydrophobic andmechanically stiffened. The fluorinated PBD is semicrystalline with amelting temperature of about 150° C., and the fluorinatedpolycyclohexadiene (PCHD) is an amorphous material with a high T_(g).Hydrogenated PCHD is known have a T_(g) between about 200° C. and about250° C., depending on microstructure. Thus, in some embodiments, thepolydienes of the presently disclosed subject matter fulfill amechanically toughening role.

III.A. Synthesis of Linear ABA Triblocks

Linear triblock copolymers of an ABA architecture, wherein A ispolybutadiene (PBD) or polyisoprene (PI) and B is polystyrene (PS), canbe prepared. The logic of starting with a simple linear architecture isthe ease of synthesis of these materials and the well-known goodmechanical properties of the ABA architecture. In some embodiments ofthe presently disclosed subject matter, these materials are made usinganionic polymerization and all-glass reactors with breakseals. In someembodiments of the presently disclosed subject matter, a doublediphenylethylene lithium-based initiator (see below) is used in benzene(with addition of lithium butoxide) at room temperature in the synthesisof the middle block.

A sample of the PS is then taken for characterization and the diene,i.e., either PBD or PI, is added to the reactor to grow the triblock. Anadvantage of this method is in allowing the synthesis of high1,4-polydiene (addition of lithium butoxide has minimal effect onmicrostructure). This synthetic approach also facilitates rigorouscharacterization of the products.

III.B. Fluorination and Sulfonation Procedures

In some embodiments of the presently disclosed subject matter,cyclohexane solutions of the styrene/diene copolymers are subjected tohexafluoropropylene oxide (HFPO) at 180° C. using a high-pressurereactor as reported by Ren, Y., et al., J. Am. Chem. Soc., 120, 6830(1998) in the presence of butylated hydroxy toluene (BHT). At thistemperature, HFPO generates difluorocarbene, which selectively adds todienic unsaturation. The fluorinated products are then isolated,characterized and subjected to sulfonation. Higher fluorine levels canbe incorporated through addition of perfluoroalkyl iodides to the dienedouble bonds, as reported by Ren. Y., et al., Macromolecules, 34, 4780(2001), in which optimized reaction conditions for modification of astyrene-butadiene diblock copolymer can lead to consumption of 95% ofthe double bonds in the diene block, while preserving the narrowmolecular weight distribution.

In some embodiments of the presently disclosed subject matter, the PSsegments are sulfonated using a SO₃/triethylphosphate complex or withacetylsulfate. The former system is most useful for carrying outexhaustive sulfonation of the PS segments, whereas the latter system iseffective for carrying out partial sulfonation. In some embodiments, thesulfonations are carried out in a chloroalkane, such as dichloroethane,at ambient or lower temperatures. For polymers containing fluorinated1,4-PBD segments, however, sulfonations are conducted on solutions athigher temperatures or on thin films of polymer due to the more limitedsolubilities of these materials.

In some embodiments, materials with initial PS volume fractions of about0.18 are provided to form PS cylinders in a polydiene matrix. Thiscomposition is formulated toward the lower end of the PS cylinder volumefraction range to accommodate some PS volume fraction increase uponsulfonation without pushing the samples out of the cylindricalmorphology. Holding the PS volume fraction as constant as possible, themolecular weight of the overall material is varied from a low of about20,000 g/mol to a high value depending upon whether (1) the polydieneblock is PBD (high of 200,000 g/mol) or (2) PCHD (high of 30,000 g/mol).The overall molecular weight of the PCHD-containing materials is limitedby synthetic difficulties in achieving PCHD block molecular weightsgreater than about 30,000 g/mol. See Hong. K. and Mays, J. W.,Macromolecules, 34, 3540 (2001); Hong, K. and Mays, J. W.,Macromolecules, 34, 782 (2001); and Hong. K., et al., Macromolecules,34, 2482 (2001).

The full molecular weight range is spanned by 4 to 5 samples for each ofthese two embodiments. For instance, for PS-PBD, the molecular weightranges from 20,000; 50,000; 100,000; 150,000; and 200,000 g/mol totalmolecular weight with PS volume fraction about 0.18 in all samples. Themolecular weight ranges from about 10,000 g/mol to about 50,000 g/molfor PS-PCHD.

Samples from these series are obtained as original PS-polydienematerials, as fluorinated materials, and as fluorinated and sulfonatedmaterials for morphology and properties evaluation.

IV. ABA Triblock Copolymer Lamellae

A series of ABA triblock copolymers are provided in which the outer Ablocks comprise polydiene and the inner B block comprises polystyrene(PS) or poly(α-methylstyrene) (PαMS). Materials with initial PS volumefractions of around 0.45 are prepared to form alternating PS/polydienelamellae. This composition is formulated toward the lower end of the PSvolume fraction range for lamellae to accommodate some PS volumefraction increase upon sulfonation without pushing the samples out ofthe lamellar morphology. Holding the PS volume fraction as constant aspossible, the molecular weight of the overall material from a low ofabout 20,000 g/mol to a high value depending upon whether the polydieneblock is (1) PBD (high of 200,000 g/mol) or (2) PCHD (high of 110,000g/mol). The full molecular weight range is spanned by 4 to 5 samples foreach of these two embodiments. For instance, for PS-PBD the molecularweight ranges from 20,000; 50,000; 100,000; 150,000; and 200,000 g/moltotal molecular weight with a PS volume fraction of 0.45 in all samples.Samples from these series are obtained as original PS-polydienematerials, as fluorinated materials, and as fluorinated and sulfonatedmaterials for morphology and properties evaluation. Molecular weightranges similar to those observed for PS-PBD are obtained for PαMS-PBD,whereas a lower molecular weight ranging from about 10,000 g/mol toabout 50,000 g/mol is obtained for PS-PCHD and PαMS-PCHD.

V. Graft Copolymer Cylinders

In some embodiments of the presently disclosed subject matter, the aimto produce a self-reinforcing rigid matrix of the fluorinated PBD(semicrystalline) or PCHD (high T_(g)) surrounding sulfonated PScylinders is addressed by starting with the following architectures ofpolydiene backbones and PS grafts: grafted PS blocks at trifunctional(comb), tetrafunctional (centipede) or hexafunctional (barbwire) branchpoints as provided in FIGS. 1A-1E. Thus, the synthesis of the initialmolecular architectures uses the chemical strategies as providedimmediately herein below for constructing well-defined branched andgrated molecular architectures in PBD-PS materials as a route toachieving these architectures in the fluorinated and sulfonatedmaterials.

Accordingly, provided herein below is an overview of the strategiesemployed to make (a) single branch point mixed arm star architectures,and (b) multigraft copolymers with regularly spaced branched points ofcontrolled functionality.

V.A. Multigraft Synthetic Strategies—General Considerations

In some embodiments of the presently disclosed subject matter, polymerbackbone segments (for example, PBD or PI) are made using the dilithiuminitiator:

Difunctional Lithium Initiator (DLi)

Accordingly, architecturally precise, multigraft block copolymers withtrifunctional, tetrafunctional, or hexafunctional branch points areproduced using the general macromonomer end-linking reaction schemeshown below:DLi+BD→LiPBDLi.

Polymer branches (for example, PS) are made using a monofunctionalanionic initiator, e.g., sec-BuLi:sec-BuLi+S→PSLi.

V.B. Comb Synthesis

In some embodiments of the presently disclosed subject matter,multigraft polymers comprising a “comb” architecture are synthesized viathe following reaction scheme:PSLi+MeSiCl₃(large excess)→(PS)(Me)SiCl₂+MeSiCl₃↑(PS)(Me)SiCl₂+LiPBDLi(small excess)→PBD[Si(PS)(Me)]_(n)PBD.

V.C. Centipede Synthesis

In some embodiments of the presently disclosed subject matter,multigraft polymers comprising a “centipede” architecture aresynthesized via the following reaction scheme:PSLi+SiCl₄(vacuum titration)→(PS)₂SiCl₂(PS)₂SiCl₂+LiPBDLi→PBD[Si(PS)₂]_(n)PBD.

V.D. Branched and Grafted Block Copolymer Molecular Architecture

In some embodiments of the presently disclosed subject matter,chlorosilane coupling agents are used to link together living PS and PBDchains, which have been synthesized anionically. The final structure isprecisely controlled with regard to the molecular weights of the PSgraft blocks and the molecular weights of the PBD connectors betweeneach grafting point. The end-linking chemistry, however, is similarkinetically to a condensation polymerization (step growth) and thusproduces a distribution of total molecular weights, i.e. there is adistribution in the total PBD backbone length and the number of PSgrafts. Previous work has demonstrated that near-monodisperse samples ofgraft copolymer with a precise number of grafts can be obtained from theoverall reaction product by solvent-nonsolvent fractionation. See Beyeret al., Macromolecules, 33, 2039 (2000).

In cases where degradation of chlorosilane-linked polymers at the branchpoint(s) occurs, more robust multigraft structures can be synthesized bymetallating anionically produced polybutadiene (or polyisoprene) withBuLi/tetramethylethylene diamine, followed by polymerization of styrenefrom the anions created along the polymer backbone. See Hadjichristidis,N. and Roovers, J. E. L., J. Polymer Sci., Polym. Phys. Ed., 16, 851(1978). This method yields well-defined materials comprising a comb-likearchitecture where branches are randomly placed along the polymerbackbone. Kennedy, J. P. and Delvaux, J. M., Adv. Polym. Sci., 38, 141(1981), previously reported superior mechanical properties forpoly(isobutylene-g-styrene)s of this architecture. Further,morphological work by Xenidou. et al., Macromolecules, 31, 7659 (1998)has shown that the constituting block copolymer principle relating graftmolecular architecture to morphology can be extended in an average senseto these more architecturally varied materials.

Fluorination and sulfonation procedures of the branched and graftedcopolymers disclosed immediately hereinabove are carried out asdescribed hereinabove for the triblock case, with modification asneeded.

Using the chlorosilane coupling approach to multigrafts, samples with PScylindrical domains in a PBD matrix with trifunctional (comb),tetrafunctional (centipede), and hexafunctional (barbwire) junctionpoint architecture can be produced. Due to the effect of branch pointfunctionality on morphology, the volume fraction range of PS in whichcylinders is produced varies as the junction point functionality varies.To produce cylinders, the trifunctional comb sample has a PS volumefraction of about 0.40; the tetrafunctional centipede has a PS volumefraction of about 0.20; and the hexafunctional barbwire has a PS volumefraction of about 0.10. Thus, these embodiments of the presentlydisclosed subject matter provide an effect on the relative size of thecylindrical domains (with respect to the matrix) for desired properties.

Further, the polycondensation reaction of macromonomers by which theregular multigraft structures are produced, yields a distribution(polydispersity index (PDI) of about 2) of molecular weight in which allspecies have the same structure per junction point, but vary in thenumber of junction points linked along the backbone. Also, fractionationcan be used to isolate different fractions with identical structure perjunction point, but different (low, middle, and high) average numbers ofjunction point per molecule. See Beyer, F. L., et al., Macromolecules,33, 2039 (2000); Uhrig, D. and Mays, J. W., Macromolecules, 35, 7182(2002); latrou. H., et al., Macromolecules, 31, 6697 (1998) andNakamura, Y., et al., Macromolecules, 33, 8323 (2000).

Although these low, middle, and high molecular weight fractions tend toform the same general morphology, cylinders for instance, they differgreatly in the degree of long-range order that can be achieved in themicrostructure. The larger the number of junction points per molecule(molecular weight), the poorer the long-range order produced. Byexamining low, middle and high molecular weight fractions of the overallstructure produced by the polycondensation of macromonomers, theinfluence of microstructural order on mechanical and transportproperties can be compared and modified as desired. For example, sampleswith a high number of junction points per molecule, which, althoughmicrophase-separated, did not display long-range order, have been foundto exhibit excellent tensile mechanical properties. See Weidisch, R., etal., Macromolecules, 34, 6333 (2001).

The following combinations of architecture, molecular weight,fluorination, and sulfonation provided in Table 1 are provided by thepresently disclosed subject matter.

TABLE 1 Representative Graft Copolymers Molecular Graft Point WeightFunctionality Fraction 3 Low PBD-PS FPBD-PS FPBD-PSS 3 Middle PBD-PSFPBD-PS FPBD-PSS 3 High PBD-PS FPBD-PS FPBD-PSS 4 Low PBD-PS FPBD-PSFPBD-PSS 4 Middle PBD-PS FPBD-PS FPBD-PSS 4 High PBD-PS FPBD-PS FPBD-PSS6 Low PBD-PS FPBD-PS FPBD-PSS 6 Middle PBD-PS FPBD-PS FPBD-PSS 6 HighPBD-PS FHBD-PS FPBD-PSS PBD = polybutadiene; PS = polystyrene; FPBD =fluorinated polybutadiene; and PSS = poly(styrene sulfonic acid).

Additional details of these synthetic strategies, including thesynthesis by analogous strategies, of the hexafunctional barbwire graftarchitecture, see Uhrig. D., and Mays, J. W., Macromolecules, 35, 7182(2002), are provided in Beyer et al., Macromolecules, 33, 2039 (2000);latrou, H., et al., Macromolecules, 31, 6697 (1998); and Chang. M. Y.,et al., Macromolecules, 35, 4437 (2002), each of which are incorporatedherein by reference in their entirety.

VI. Statistical Copolymers of 1,3-cyclohexadiene and α-methylstyrene

Statistical copolymers of 1,3-cyclohexadiene and α-methylstyrene (aMS)provide another embodiment of the presently disclosed subject matter,which in some embodiments can be used at higher temperatures. The basicstrategy, shown in Scheme 2, is similar to that disclosed hereinabove.As shown in Scheme 2, the polycyclohexadiene (PCHD) units in thecopolymer are fluorinated using difluorocarbene, followed by sulfonationof PαMS. Based on the known characteristics of PCHD (T_(g) of about 150°C., semicrystalline, ring structure) this material is expected to form asemicrystalline matrix of good thermal stability and high T_(g). ThePαMS segments are sulfonated (PαMSS) to facilitate proton transport.

The choice of αMS and a statistical, rather than block, copolymer isbased, in part, on two reasons. First, the substitution of the tertiaryhydrogen in polystyrene, which is susceptible to oxidative attack by O₂or H₂O₂, with a methyl group provides a more stable material in membraneapplications. Second, the tendency of PαMS chains, when they do degrade,to do so by “unzipping” to monomer, is prevented. The more weaklyphase-separated morphologies formed by these systems can, as discussedhereinabove, offer permeability characteristics favorable for use inmethanol fuel cells, coupled with improved thermal stability. Thesematerials also are potentially low cost, because commercial productionof the cyclohexadiene monomer is being considered.

VII. Membranes Based on Poly(cyclohexadiene)

In some embodiments of the presently disclosed subject matter, theunusual chemical nature of poly(cyclohexadiene) (PCHD) provides a uniquemembrane based entirely on this polymer following severalpostpolymerization modifications as shown in Scheme 3.

Films of the desired thickness are cast from PCHD solutions (ease ofprocessing). The polymer is then covalently crosslinked (polydienevulcanization, e.g., with peroxides), thus stabilizing the size andshape of the membrane. A chemical dehydrogenation step to aromatize thepolymer (i.e., converting it into poly(phenylene)) using p-chloranil,2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), or related reagents isthen carried out, see Williamson, D. T., et al., ACS Polym. Preprints,43(2), 1201 (2002), followed by sulfonation. For example, thesulfonation of low molecular weight, aromatized PCHD results in a watersoluble product.

Thus, the presently disclosed subject matter provides a method offorming a proton exchange membrane, the method comprising:

-   -   (a) casting a polymeric film from a solution of        poly(cyclohexadiene);    -   (b) crosslinking the polymeric film to form a crosslinked        polymeric film;    -   (c) aromatizing the polymeric film to form a poly(phenylene);        and    -   (d) sulfonating the poly(phenylene).

The resulting material is covalently and ionically crosslinked, and hasa highly aromatic structure, which imparts excellent thermo-oxidative,chemical, and dimensional stability to the membrane. Note that even ifcomplete aromatization of the diene is not carried out, any residualdouble bonds will be eliminated during sulfonation (alkene sulfonation).Combined covalent and ionic crosslinking of aromatic structures leads tomembranes of improved dimensional stability with the potential forreduced methanol permeation. Thus, membranes comprising the currentlydisclosed materials exhibit outstanding potential for use in methanolfuel cells at temperatures well above 100° C. A photograph of apresently disclosed cross-linked poly(1,3-cyclohexadiene) (PHCD)membrane is shown in FIG. 2.

VIII. Self Assembling Barrier Elastomer (SABrE) Materials

Self Assembling Barrier Elastomer (SABrE) materials typically compriseblock or graft copolymers of sulfonated polystyrene and polyisobutylene,which have elastomeric mechanical properties. The sulfonated polystyreneself-assembles to form nanometer size hydrophilic domains withcylindrical geometries that provide pathways for water transport (andthus breathability) across the hydrophobic butyl rubber(polyisobutylene) matrix. Due to their extremely small size and to theirchemical functionality, these hydrophilic channels are not accessible tochemical and biological threats. Thus, SABrE materials exhibit thecharacteristic of selective transport. Further, when the SABrE materialis based on a graft copolymer comprising many tetrafunctional graftpoints per molecule, then the material has exceptional mechanicalproperties.

Such materials can be used as a fabric, which in some embodiments can bea barrier fabric, for example for use as breathable chemical-biologicalprotective barrier clothing for military personnel, emergency responseteams, industrial and/or agricultural workers and/or other applications,and healthcare professionals. Indeed, any article or item that isdesired to be covered can be covered, such as but not limited to plants(indeed, any form of vegetation) or other agricultural applications inan environment where coverage would be of interest for at least a periodof time, and industrial equipment that is maintained in an environmentwhere coverage would be desirable for at least a period of time.Standard protective clothing is made largely from butyl rubber (BR), amaterial whose impermeability provides an excellent level of protection,but also traps heat and moisture inside the garments. BR garments alsoare bulky and limit dexterity. For example, a particular problem withgloves made from BR materials is that they constrain hand movement. In adesert combat environment these problems could result in more thansimple discomfort and inconvenience.

The fluorinated and sulfonated materials of the presently disclosedsubject matter are directly applicable to SABrE materials. Microphaseseparated block copolymers have the potential to economically produceprotective fabrics, which in some embodiments act as barrier materials,with improved breathability, comfort and wear resistance. A strategy fordoing this is to exploit the excellent barrier properties of animpermeable polymer matrix, while at the same time blending in blockcopolymers which microphase separate to form membrane spanning channels.Such block copolymers include materials comprising sulfonated PS blocks,

Variations in the molecular architecture of graft copolymers can bemanipulated to control the nano-scale structure (morphology) and theability to form long-range order during self-assembly. Synthetictechniques have been developed to produce the precisely controlledmolecular architectures, some of which are provided in FIGS. 1A-1E.Further, such well-defined molecular architecture is related tomorphology and properties. As a result, morphology and long-range orderof microphase separated structures can be controlled through moleculardesign.

The presently disclosed subject matter utilizes this control ofmorphology to tailor properties of fluorinated ionomer materials whichshare some of the block and grafted architectural features of previouslyreported non-fluorinated materials.

To optimize performance, the size, shape and symmetry, and overallvolume fraction of different types of domains are controlledindependently. This independent control, however, is not possible withconventional linear AB diblock copolymers and ABA triblock copolymersfor which the nanophase separated morphology which forms (e.g., spheres,cylinders, cubic bicontinuous gyroid, or lamella) is tied directly tothe relative volume fractions of the two block materials. For example,if an application such as SABrE demands a material withmicrophase-separated nanometer length scale cylinders in which thecomponent comprising the conductive cylindrical domain makes up over 50volume percent of the material, linear block copolymers would not bepreferred.

One way to uncouple block copolymer morphology from its rigid dependenceon component volume fractions is to vary molecule architecture. By wayof example, for mixed arm star architectures such as the A₂B shown inFIG. 1A, the asymmetry factor is: ε=(n_(A)/n_(B))/(ζ_(A)/ζ_(B)), wherein(n_(A)/n_(B)) is the ratio of arm numbers of the two block types andrepresents the asymmetry due to the architecture and the conformationalasymmetry between the two block materials is expressed by the ratio,(ζ_(A)/ζ_(B)), wherein ζ_(i) is the ratio of segmental volume to thesquare of statistical segment length for the block material i.

Methods to determine the architectural asymmetry part of a generalizedasymmetry parameter for any of the various graft copolymer architecturesencountered have been developed. Further, these methods have been testedwith extensive morphological studies of model star and graft shapedblock copolymers. Also, complex graft copolymer architectures withmultiple grafting points (e.g., FIGS. 1C-1E) can be understoodmorphologically by analogy to fundamental building blocks defined as theaverage structure per junction.

This fundamental component of a larger graft molecular architecture isreferred to as the “constituting block copolymer.” For a graft copolymerwith a backbone of A and blocks of B joined to the backbone attrifunctional branch points (see, e.g., FIG. 1C), the constituting blockcopolymer is an A₂B single graft copolymer (see FIG. 1A).

Previous characterization data on complex graft copolymer architectureswith multiple grafting points has been fit into the framework of atheoretical morphology diagram (see FIG. 3) calculated by Milner. S. T.,Macromolecules, 27, 2333 (1994), whose analysis predicts morphology as afunction of composition and molecular asymmetry (architecture) formaterials with a single junction point. For example, at ε=1, the Milnerdiagram models linear, conformationally symmetric, AB diblock behaviorwith symmetric morphology windows around φ_(B)=0.5. As the number ofarms of one species increase relative to the other, however, themorphological behavior can become strongly asymmetric with respect tovolume fraction. This behavior allows the sought after uncoupling ofmorphology from volume fraction to be achieved. Thus, the morphology canbe varied independently of volume fraction by adjusting the moleculararchitecture. Milner's theory is not strictly applicable to morecomplex, multiple graft copolymer materials, however. The use of thebuilding block principle of the constituting block copolymer tounderstand the morphological behavior of multiple graft materials bymapping them back to the more well-understood behavior of single graftmaterials has been required. These ideas have been used to develop arational framework for predicting the morphologies of all the types ofmolecular architecture shown in FIGS. 1A-1E.

As disclosed hereinabove, FIG. 3 shows experimental data from previouswork on a range of different branched molecular architectures plotted onthe morphology diagram. This morphology diagram now provides thebackground necessary to move forward on materials with similararchitectures, but dramatically different fluorinated and charged blockmaterials for different applications, such as fuel cells.

IX. Templates for Sol-Gel Polymerization

In some embodiments of the presently disclosed subject matter,phase-separated ionomers, such as those described herein, can act astemplates for sol-gel polymerizations of metal alkoxides to generatenanostructured membranes. Previous studies involving NAFION® materialhave shown that H₂O molecules hydrogen bond to ≡SiOH groups on insertedsilicate nanostructures and H⁺ hopping is possible along percolatedhydration nanostructures. NAFION®/silicate membranes have greaterinternal polarity and hydrative capacity than NAFION®-H⁺ membranes dueto ≡SiOH functionalities. See Deng. Q., et al., Chem. Mater. 7, 2259(1995); Deng, Q., et al., J. Sol-Gel Sci. & Technol. 7, 177 (1996);Deng, Q., et al., J. Polymer Sci. B: Polymer Phys. 34, 1917-1923 (1996);and Deng. Q., et al., Them. Mater. 9, 36 (1997).

Also, sulfonated poly(styrene-isobutylene-styrene) block copolymers andcommercial KRATON® triblock copolymers can induce domain-targetedsol-gel polymerizations in styrenic regions during film formationresulting in self-assembled organic/inorganic nanostructured membranes.The water affinity of these block copolymers increases with sulfonation,but dramatically increases after silicate nanophase incorporation. Thereare cases where sulfonation can induce morphological transformations,which is another variable available for structural tailoring formembrane optimization.

X. Representative Applications

In some embodiments, the presently disclosed copolymers of fluorinatedpolydienes and sulfonated polystyrene and, in some embodiments, thepresently disclosed cross-linked poly(1,3-cyclohexadiene (PCHD) polymerscan be used in the following representative applications, including, butnot limited to, a proton exchange membrane for a fuel cell, apolyelectrolyte for a battery, and a fabric, for example, for use asbreathable chemical-biological protective clothing.

X.A. Proton Exchange Membrane

In some embodiments, the presently disclosed copolymers of fluorinatedpolydienes and sulfonated polystyrene and the presently disclosedcross-linked poly(1,3-cyclohexadiene (PCHD) polymers can be used as aproton exchange membrane in an electrochemical cell, for example, a fuelcell.

Referring now to FIG. 4, fuel cell 400 comprises proton exchangemembrane 402, which, in some embodiments comprises a presently disclosedcopolymer of a fluorinated polydiene and a sulfonated polystyrene, and,in some embodiments, comprises a presently disclosed cross-linkedpoly(1,3-cyclohexadiene) polymer.

Referring again to FIG. 4, proton exchange membrane 402 is operationallypositioned between and contacted with first catalyst layer 404, e.g., ananodic catalyst layer, and second catalyst layer 406, e.g., a cathodiccatalyst layer, which are contacted with first electrode 408, e.g., ananodic electrode, and second electrode 410, e.g., a cathodic electrode,respectively. The body of fuel cell 400 is formed by layers or plates412 and 414, which comprise channels 416 and 418 that are used totransport fuel and/or waste products to and from first electrode 408 andsecond electrode 410. First electrode 408 and second electrode 410 arein conductive communication with electrical output connection E_(o).

X.B. Polyelectrolyte

Polyelectrolytes can form a multitude of structures at various lengthscales in solution and can display a variety of properties not found inneutral polymers. The properties of these structures are controlled bymany parameters, such as the inherent characteristics of themacromolecular backbone, charge types and locations, temperature, ionicstrength, pH, and the like.

The presently disclosed copolymers of a fluorinated polydiene and asulfonated polystyrene and the presently disclosed sulfonatedcross-linked poly(1,3-cyclohexadiene) polymer provide a polyelectrolytefor use in, for example, a battery. More particularly, the presentlydisclosed sulfonated cross-linked poly(1,3-cyclohexadiene) polymerprovides a well-defined polyelectrolyte with a lower flexibility thansynthetic polyelectrolytes known in the art, due to the incorporation ofthe poly(1,3-cyclohexadiene) ring into the polymer backbone.

X.C. Fabric

In some embodiments, the presently disclosed subject matter provides afabric, which in some embodiments comprises a barrier fabric, comprisingthe presently disclosed copolymers of fluorinated polydienes andsulfonated polystyrene and, in some embodiments, the presently disclosedcross-linked poly(1,3-cyclohexadiene (PCHD) polymers.

Such materials can be used as a barrier fabric, for example for use asbreathable chemical-biological protective barrier clothing to protectmilitary personnel, emergency response teams, industrial and/oragricultural workers, and healthcare professionals from chemical and/orbiological agents, including hazardous and/or toxic chemicals andmicroorganisms, such as, but not limited to, chemical-biological warfareagents, viruses, bacteria, blood-borne pathogens, air-borne pathogens,industrial chemicals, and agricultural chemicals, in liquid, vapor, andaerosol forms. Further, such materials allow perspiration products toescape from, for example, a body, while preventing the penetrationand/or transport of the aforementioned hazardous and/or toxic materials.

Further, in some embodiments, such barrier fabric can be used to protectagricultural products, including living and cultivated vegetativeproducts, from, for example, exposure to natural pathogens, such asfungi, chemical and/or biological pathogens, and frost. In someembodiments, such barrier fabric can be used as a “weed barrier,” which,for example, impedes the growth of undesired vegetative species, whileretaining moisture in the soil.

X.D. Sol-Gel Templates

Sol-gel syntheses can be used to produce a variety of inorganic networksfrom silicon or metal alkoxide monomer precursors. In a typical sol-gelsynthesis, a soluble precursor molecule, e.g., a metal alkoxide, ishydrolyzed to form a dispersion of colloidal particles (the sol).Further reaction causes bonds to form between the sol particlesresulting in an infinite network of particles in a continuous liquidphase (the gel). The gel typically is then heated to yield the desiredmaterials. The precursors for synthesizing these colloids typicallycomprise a metal or metalloid element surrounded by a reactive ligand.Metal alkoxides are particularly useful in sol-gel syntheses becausethey readily react with water. The most commonly used alkoxides are thealkoxysilanes, such as tetramethoxy silane and tetraethoxysilane. Otheralkoxides, such as aluminates, titanates, and borates also are commonlyused in sol-gel processes.

Membranes, such as porous alumina membranes and etched polymericmembranes, can be used as templates for sol-gel syntheses of, forexample, micro- and nanostructures. As provided hereinabove in sectionIX, in some embodiments of the presently disclosed subject matter,phase-separated ionomers, such as those described herein, can act astemplates for sol-gel polymerizations of metal alkoxides to generatenanostructured membranes.

EXAMPLES

The following Examples have been included to provide guidance to one ofordinary skill in the art for practicing representative embodiments ofthe presently disclosed subject matter. In light of the presentdisclosure and the general level of skill in the art, those of skill canappreciate that the following Examples are intended to be exemplary onlyand that numerous changes, modifications, and alterations can beemployed without departing. from the scope of the presently disclosedsubject matter.

Example 1 Synthesis of Copolymers

Unless otherwise noted, polymers were synthesized under an inertatmosphere. High vacuum techniques were sometimes employed and allsolvents and monomers were purified according to anionic polymerizationstandards as described in the literature. See Hadjichristidis, N., etal., J. Polym. Sci., Polym. Chem. Ed., 38, 3211 (2000). A difunctionalinitiator DLI was synthesized by the 2-fold addition of sec-butyllithiumto 1,3-bis(1-phenylethenyl)benzene as reported previously (Uhrig, D. andMays, J., Macromolecules, 35, 7182 (2002) and Tung, L. H., and Lo, T.Y.-S., Macromolecules, 27, 2219 (1994)) and stored as a 0.1 M solutionin benzene. Prior to use, styrene monomer was distilled from calciumhydride under vacuum and stored at −20° C. under pressurized argon.Isoprene monomer was distilled from calcium hydride, and then distilledfrom 1.0 M dibutylmagnesium solution just before use. 1,3-Cyclohexadiene(1,3-CHD, Aldrich, 97%) was cleaned by treatment over CaH₂, sodiummirror (three times), and finally n-BuLi or MgBu₂.

Example 1.1 Synthesis of an Isoprene-Styrene-Isoprene (ISI) TriblockCopolymer

A 250 mL round bottom flask with a magnetic stir bar was dried in a 150°C. oven over 24 hours, then sealed with a septum and purged/cooled withargon. Cyclohexane (150 mL) was cannulated into the flask, followed by2.2 mL (0.22 mmol) DLi difunctional initiator and 1.2 mL (14.8 mmol)THF. The resulting mixture was stirred for 30 minutes. Styrene monomer(2.0 mL, 17.4 mmol) was charged into the flask and polymerized at roomtemperature for 2 hours. Then, isoprene monomer (10.0 mL, 76.9 mmol) wascharged into the flask and the flask was warmed to 50° C. The resultingmixture was stirred at room temperature overnight. The polymerizationwas terminated with degassed methanol, and the ISI triblock copolymerwas collected by precipitation in methanol containing 0.2% BHT.Solvent/nonsolvent (toluene/methanol) fractionation was used to removethe diblock contaminants.

Example 1.2 Synthesis of a PS-PCHD Diblock Copolymer

PS-PCHD diblocks are prepared by either polymerizing 1,3-CHD first,followed by addition of styrene, or by polymerizing styrene first,followed by addition of 1,3-CHD. In a typical experiment, about 85 mLpurified benzene was distilled into an evacuated reactor with attachedampoules containing all the necessary purified reagents. The reactor wasremoved from the vacuum line by heat-sealing after degassing. A 5.5 mLaliquot of sec-BuLi (9.7×10⁻⁵ mmol/mL in hexanes) was added followed by2.3 g (0.022 mol) styrene. The polymerization started right away (asevidenced by a deep red color) and was allowed to continue for 6 hoursbefore taking an aliquot (approximately 1 mL) for characterization. SECand MALDI-TOF-MS results indicated a molecular weight of 4.52 kg/molwith a polydispersity of 1.08. About 2.5 mL of DABCO (3.2×10⁻⁴ mol/mL inbenzene) was introduced into the reactor through a break-seal. Afterstirring about 5 minutes at room temperature, 6.4 g (0.08 mol) of1,3-CHD was added from another ampoule. The solution turned goldenyellow and was allowed to continue to polymerize for another 6 hoursbefore the reaction was terminated with degassed methanol. The finalproduct had a weight-average molecular weight (Mw) of 18.6 kg/mol (asindicated by MALLS), a number-average molecular weight (Mn) of 15.4kg/mol (from MALDI-TOF analysis), a polydispersity (Mw/Mn) of 1.03, anda composition of PCHD with 66.0 wt % (as determined by NMR).

Example 1.3 Synthesis of Multigraft Copolymers

Comb Synthesis. An all-glass linking reactor was charged withapproximately 2 mL of MeSiCl₃ in a small quantity of benzene. Anapproximately 5% w/v solution of PSLi in benzene was added to the silaneso that the concentration of silane versus the concentration ofcarbon-lithium bonds, [silane]/[CLi],=100 while the reactor contentswere stirred briskly in a 0° C. bath. The solution was allowed to warmto room temperature following the addition.

The contents of the reactor were distilled until the solution was tooviscous to stir. Fresh benzene was added to make an approximately 10%w/v solution, and the contents were well mixed. This sequence wasrepeated twice more. The reactor was then left open to a high vacuum atroom temperature for one week. Finally, benzene was added to make anapproximately 3% w/v solution.

LiPILi was prepared as an approximately 3% w/v sqlution in benzene,initiated from DLI in the presence of sec-BuOLi ([COLi]/[CLi]=7). TheLiPILi solution and the (PS)MeSiCl₂ from the linking reactor wereadjusted to a stoichiometric ratio of [CLi]/[SiCl]=1.2, and thesolutions were mixed. After 1 day, several milliliters of THF were added(approximately 0.5% v/v of the finally resulting solution; THF/Li=100).

Centipede Synthesis. An all-glass linking reactor was charged with 0.200mmol of SiCl₄ in a small quantity of hexane and benzene. Anapproximately 3% w/v solution of PSLi was incrementally added to thesilane. The first addition was made such that approximately 0.27 mmol ofPSLi was added quickly to the chilled reactor (0° C. bath, colder thanthe flask of PSLi at 20° C.) with brisk stirring. After the firstaddition was made, the reactor was allowed to warm slowly to 20° C.(isothermic with the flask of PSLi), and further dropwise additions ofPSLi were made. The progress of the linking reaction was monitored byremoving small aliquots from the reactor and analyzing them with SEC.After approximately 2 equivalents of PSLi (approximately 0.40 mmol) hadbeen added to the reactor, and more importantly the end point was judgedby SEC, the titration was stopped.

An approximately 3% w/v solution of LiPILi in benzene and the (PS)₂SiCl₂in the linking reactor were mixed in a stoichiometric ratio of[CLi]/[SiCl]=1.2. After 1 day THF was added (approximately 0.5% v/v ofthe finally resulting solution; THF/Li=100).

Barbwire Synthesis. An all-glass linking reactor was charged with 0.200mmol of 1,6-bis(trichlorosilyl)hexane (hexachlorosilane) in a smallquantity of hexane and benzene. An approximately 3% w/v solution of PSLiwas incrementally added to the silane. The first addition was made suchthat approximately 2 equivalents (approximately 0.40 mmol) was added tothe reactor. After the first addition, approximately 0.5 mL of THF wasslowly distilled into the reactor (less than 0.5% v/v of the resultantlinking solution; THF/Li=30). Further additions were made slowly to acalculated (stoichiometry of reagents and concentration of PSLi)stopping point of approximately 4.3 equivalents of PSLi (approximately0.87 mmol). The progress of the linking reaction was monitored byremoving small aliquots from the reactor and analyzing them via SEC. Itwas noticed that after addition of beyond approximately 3.7 equivalentsof PSLi, the color in the linking reactor steadily grew more intenselygolden.

An approximately 3% w/v solution of LiPILi in benzene and the contentsof the linking reactor were mixed in a stoichiometric ratio of[CLi]/[SiCl]=1.2. After 1 day THF was added (approximately 0.5% v/v ofthe finally resulting solution; THF/Li=100).

Workup and Fractionation. The linking solutions were permitted to reactfor 3 weeks before quenching. The raw final polymers were stabilizedwith BHT and precipitated with a large excess of methanol. Fractionationwas performed using toluene/methanol as the solvent/nonsolvent pair.

Additional details for the synthesis of the presently disclosedpoly(isoprene-graft-styrene) copolymers are provided in Uhrig, D., andMays, J. W., Macromolecules, 35, 7182 (2002), the disclosure of which isincorporated herein by reference in its entirety.

Example 1.4 Synthesis of Statistical Copolymers of 1,3-Cyclohexadieneand α-Methylstyrene

The general procedure for the synthesis of statistical copolymers of1,3-cyclohexadiene and α-methylstyrene (aMS) is provided hereinabove inScheme 2. Also as shown in Scheme 3, the polycyclohexadiene (PCHD) unitsin the copolymer are fluorinated using difluorocarbene, followed bysulfonation of PαMS.

Example 2 Fluorination and Sulfonation Procedures Example 2.1 GeneralConsiderations

Fluorination of polydienes by generation of difluorocarbene has beenreported by Cais, R. B., et al., Macromolecules, 19, 595 (1986), usingPhHgCF₃ as the fluorine source, and by Thomson, M. W., Macromolecules,22, 481 (1989), via irradiation of chlorofluorocarbons. Further, Ren,Y., et al., J. Am. Chem. Soc., 120, 6830 (1998), have reported a facilemethod for fluorination of polydienes based upon difluorocarbeneaddition. This reaction employs the relatively inexpensivehexafluoropropylene oxide as a reagent and does not lead to chainscission or crosslinking.

An example of the post-polymerization fluorination of polybutadiene(PBD) and sulfonation of polystyrene (PS) in a PS-PBD block copolymer isprovided hereinabove in Scheme 1. After fluorination of the polydiene,e.g., polybutadiene, component, the polystyrene segments can besulfonated using reagents, such as acetyl sulfate or sulfur trioxide, toform poly(styrene sulfonic acid) (PSS).

Example 2.2 Fluorination of ISI Triblock Copolymer

The ISI triblock copolymer (3.0 g, 35 mmol double bond content) and 0.4g BHT was dissolved in 120 mL pretreated cyclohexane and charged into aParr reactor. The Parr reactor was purged with argon and cooled withliquid nitrogen. Hexafluoropropylene oxide (HFPO, 98 g, 590 mmol) wastransferred into the Parr reactor from a tank using a regulator andtubing. The Parr reactor was warmed to 50° C. and stirred for 30 min.The Parr reactor was heated to 180° C. and slowly stirred for anadditional 20 hours. The pressure was released slowly through a sodiumhydroxide solution after the reactor was cooled to room temperature. Thesolid material in the Parr reactor was dissolved in chloroform,un-dissolved material was removed by filtration, and the filteredsolution was precipitated with methanol. The obtained precipitate wasdried under vacuum at room temperature.

Proton NMR indicated the quantitative fluorination of the polyisopreneblock. GPC characterization revealed that the average molecular weightof the triblock copolymer had changed from 43,900 g/mol beforefluorination to 22,600 g/mol after fluorination, and the polydispersityindex (PDI) went from 1.23 to 1.55.

Example 2.3 Sulfonation of Fluorinated ISI Triblock Copolymer

Fluorinated ISI triblock copolymer (1.8 g) was dissolved in 20 mLdichloroethane (DCE). Sulfuric acid (2.5 mL) and acetic anhydride (3.7mL) were mixed in a flask, which was then cooled in an ice bath. Thesulfuric acid/acetic anhydride mixture was added drop-wise through anaddition funnel into the polymer solution at room temperature. Theresulting solution was stirred at room temperature for 20 hours. DCE wasremoved by rotary evaporation. The remaining residue was dissolved in 50mL distilled water and then titrated to a pH of about 7 with 10% sodiumhydroxide solution. The neutralized solution was purified by dialysis indistilled water several times (MW cutoff of the dialysis tube=1,000g/mol). The water was removed by rotary evaporation. The remainingdark-brown material was dried under vacuum at room temperature.

Example 3 Molecular Characterization of the Synthetic Products Example3.1 Characterization of Linear and Branched Styrene/Diene Copolymers

Samples of all polymer segments are taken during the reactions (wheneverpossible) to allow for the independent characterization of the precursorsegments and the final block copolymers by absolute molecular weightmethods such as osmometry, matrix assisted laser desorption ionizationtime-of-flight mass spectrometry (MALDI-TOF-MS), and light scattering,as well as by gel permeation chromatography (GPC), nuclear magneticresonance (NMR) spectrometry, and infrared (IR) spectrometry.

Example 3.2 Characterization of Materials After Fluorination andSulfonation

After the fluorination reactions, the polymer is isolated andcharacterized by ¹H and ¹⁹F NMR and GPC to check for complete reactionof the diene and to assure that degradation has not occurred. GPC attemperatures up to 220° C. is carried out, with light scatteringdetection, even for specimens exhibiting crystallinity at lowertemperatures. After sulfonation, the products are characterized forextent of sulfonation by elemental analysis. The sulfonation conditionschosen have been shown to yield little if any degradation of precursorpolymers. Thus, in some embodiments, the molecular architectures anddegrees of polymerization should not be altered from their precursorstates.

Example 3.3 Characterization of Conformational Asymmetry of FluorinatedPolydienes and Partially Sulfonated Polystyrene

Light scattering and viscometry experiments are used to estimatepersistence lengths of the individual polymer segments to calculateconformational asymmetry. Bulk densities are measured for fluorinatedpolydienes and for sulfonated polystyrenes using standard ASTM methods.

Example 4 Preparation of a Crosslinked Poly(1,3-cyclohexadiene) MembraneExample 4.1 Synthesis of Linear Poly(1.3-cyclohexadiene) (PCHD)

Poly(1,3-cyclohexadiene) (PCHD) was synthesized under inert gasatmosphere. The materials used in the synthesis of PCHD were prepared asfollows. 1,3-cyclohexadiene monomer was purified by stirring withfine-grounded calcium hydride over 24 hours then distilled under argon.1,4-Diazabicyclo[2,2,2]ocatane (DABCO) was sublimed under vacuum thendiluted in benzene. Cyclohexane was stirred with sulfuric acid for 24hours and then separated into a cyclohexane fraction. The cyclohexanewas washed with water, 10% sodium hydroxide solution, water again, driedwith calcium chloride, then distilled from sodium metal and stored underargon. Benzene was purified via the same procedure as cyclohexane.Sec-Butyl lithium (sec-BuLi) (Aldrich, 1.4 M) was used as received.

A typical procedure for synthesizing PCHD is as follows. A 250 mL roundbottom flask with a magnetic stir bar was dried in an oven heated to150° C. for 24 hours, then sealed with a septum and purged/cooled withargon flow. 100 mL of pretreated benzene (or cyclohexane) was chargedthrough a double tipped needle. 1,3-Cyclohexdiene monomer (10 mL, 0.105mmol) was charged into the flask. DABCO in benzene (approximately 1.7 M,1.5 mL, 2.55 mmol) was charged into the flask by using a syringe. Themixture was titrated with several drops of sec-BuLi to a very pale colorand then the desired amount of sec-BuLi (0.6 mL, 0.84 mmol) wasimmediately injected. The mixture was stirred at room temperature for3-4 hours, then terminated with several drops of degassed methanol. Thepolymer was collected by precipitating in methanol containing 0.2% BHT.The obtained polymer was dried under vacuum at room temperature and thenstored at −20° C.

Example 4.2 Synthesis of a Cross-Linked Poly(1.3-cyclohexadiene) (PCHD)Membrane

A typical procedure for the synthesis of a cross-linkedpoly(1,3-cyclohexadiene) (PCHD) membrane is as follows. In a 100-mLround bottom flask with a magnetic stir bar, 3 g of PCHD (37.5 mmoldouble bond units) was dissolved in 20 mL of toluene and then thedesired amount of sulfur monochloride (0.15 mL, 1.87 mmol) was added.The ratio of PCHD repeat units to sulfur monochloride was controlledaround 20:1 mol/mol. The mixture was stirred until the viscosity of themixture increased. The mixture was pulled out onto a Teflon disc (10 cmin diameter) before forming a gel. Most of the solvent was evaporatedunder nitrogen flow to form the cross-linked membrane. After themembrane was tough enough to handle, but was not totally dry, themembrane was peeled off carefully.

Example 4.3 Synthesis of an Aromatized Cross-LinkedPoly(1.3-cyclohexadiene (PCHD) Membrane

A typical procedure for the synthesis of an aromatized cross-linkedpoly(1,3-cyclohexadiene (PCHD) membrane is as follows. The cross-linkedPCHD membrane was cut into a 2.5′×2.5′ square sheet and placed into athree necked, 1,000-mL reaction vessel (diameter 10 cm) containing amagnetic stir bar and a customized porous ceramic supporter. Themembrane was placed flat on the supporter. Xylene was added into thereaction vessel to submerge the PCHD membrane. The desired amount ofp-chloranil was dissolved into the xylene then the temperature wasraised to 130° C. The reaction was performed 24 hours under nitrogenprotection. The obtained membrane was washed with different solvents(isopropanol, THF, etc) to remove the p-chloranil. The membrane wascarefully dried for further use.

Example 4.4 Sulfonation of an Aromatized/Non-Aromatized Cross-LinkedPoly(1.3-cyclohexadiene) (PCHD) Membrane

A typical procedure for the sulfonation of an aromatized/non-aromatizedcross-linked poly(1,3-cyclohexadiene) (PCHD) membrane is reported asfollows. The PCHD membrane (aromatized or non-aromatized) was placedflat on a ceramic supporter in a three-necked, 1,000-ml reaction vessel(diameter 10 cm) containing a magnetic stir bar. Dichloroethane wasadded into the vessel to submerge the membrane. Sulfuric acid and aceticanhydride mixture in a 1:1.5 v/v ratio was added drop wise into thevessel. The reactions were kept going up to 24 hours, and thetemperature varied for different sulfonation reactions from roomtemperature to 100° C. to vary the degree of sulfonation. The obtainedmembrane was washed carefully with distilled water, then stored in aplastic bag containing a small amount of moisture.

Example 4.5 Characterization of the Cross-LinkedPoly(1.3-cyclohexadiene) (PCHD) Membranes

The molecular weights and polydispersities of the linear PCHD precursorsfor cross-linking were characterized via gel permeation chromatography(GPC). The molecular weights of all the linear samples are about 10,000g/mol, with a polydispersity of about 1.1-1.2.

Proton NMR shows that the linear PCHD samples have a highly 1,4microstructure.

The thermal stability of the presently disclosed cross-linked PCHDmembrane, aromatized PCHD membrane, and sulfonated PCHD membrane with orwithout aromatization were studied via DSC and TGA. An example of thethermal analysis of a presently disclosed cross-linked PCHD membrane isprovided in FIG. 5.

Fourier transform infrared (FTIR) spectrometry was used to investigatethe chemical change on the surface of the presently disclosedcross-linked PCHD membranes before and after aromatization andsulfonation. FIG. 6A shows a representative FTIR spectrum of a presentlydisclosed cross-linked PCHD membrane and FIG. 6B shows a representativeFTIR spectrum of a presently disclosed sulfonated, aromatizedcross-linked PCHD membrane.

Scanning electron microscopy (SEM) was used to study the surface defects(cracks) of the cross-linked PCHD membranes before and afteraromatization and sulfonation. FIG. 7A shows an SEM micrograph of across-linked PCHD membrane before sulfonation and FIG. 7B shows an SEMmicrograph of a cross-linked PCHD membrane after sulfonation.

The degree of sulfonation of all sulfonated samples was characterizedbased on the elemental analysis that focused on carbon and sulfurcontents to all membrane samples before and after sulfonation.

The water uptake of sulfonated membranes was characterized by the weightdifference between a thoroughly dried membrane and a thoroughlymoisturized membrane.

Example 5 General Methods of Morphological Characterization

Morphological characterization is a key step in any effort to relatenanoscale structure to properties. In some embodiments, the presentlydisclosed subject matter seeks to determine how fluorination andsubsequent sulfonation affect the morphological self-assembly of thematerials. To address this question, the morphology of the initialPS-PBD material is compared to the fluorinated PS-FPBD material andfinally to the fluorinated and sulfonated PSS-FPBD. Morphologicalcharacterization of these materials utilizes real-space, transmissionelectron microscope (TEM) imaging and reciprocal-space small anglescattering (SAXS and/or SANS) techniques. Morphological study of thePS-PBD materials utilizes established techniques and protocols.

The following procedure is a representative method by which themorphology of a block or graft copolymer is evaluated. This procedure isthe same general approach that has been employed in previous blockcopolymer research on PS-polydiene materials to produce a samplerepresentative of the equilibrium morphology, and to evaluate thatmorphology. See Gido. S. P., et al., Macromolecules, 29, 7022 (1996);Gido. S. P., et al., Macromolecules, 30, 6771 (1997); Pochan. D. J., etal., Macromolecules, 29, 5091 (1996); Pochan. D. J., et al., J. PolymerSci.: Part B, Polymer Physics, 35, 2629 (1997); Lee, C., et al., J.Chem. Phys., 107, 6460 (1997); Lee, C., et al., Macromolecules, 30, 3732(1997); Lee, C., et al., Polymer, 19, 4631 (1998); Xenidou. M., et al.,Macromolecules, 31, 7659 (1998); Beyer, F. L., et al., Macromolecules,30, 2373 (1997); Beyer. F. L., et al., Macromolecules, 32, 6604 (1999);Beyer. F. L., et al., J. Polymer Sci.: Part B, Polymer Physics, 37, 3392(1999); Beyer. F. L., et al., Macromolecules, 33, 2039 (2000); Burgaz.E., et al., Macromolecules, 33, 8739-8745 (2000); Alward, D. B., et al.,Macromolecules, 19, 215 (1986); Thomas, B. L., et al., Macromolecules,20, 2934 (1987); Thomas, B. L., Macromolecules, 19, 2197 (1986); Gido,S. P., et al., Macromolecules, 26, 4506 (1993); and Winey, K. I., etal., J. Chem. Phys., 95, 9367 (1991).

Solid films of the block or graft copolymer material, approximately 1-to 3-mm thick, are cast from solution. Toluene is the standardnon-preferential solvent for polystyrene (PS) and polyisoprene (PI).Casting from other solvents that are selective for either PS or PI canresult in shifts in morphology away from that which the molecule itselfwould prefer. The degree of long-range order in the samples can then beincreased by thermal annealing at about 120° C. These casting andannealing conditions have been found to promote self-assembly ofwell-ordered, nanostructured morphologies in previous studies of graftcopolymers.

After annealing, ultrathin sections approximately 30-80 nm thick areprepared for TEM observation by cryoultramicrotoming. The sections ofPS-PBD materials are stained in OsO₄ vapors for about four hours toreact with the PBD block double bonds, rendering these blocks dark inTEM imaging via mass thickness contrast. See Kato, K., PolymerEngineering and Science, 8, 38 (1967); and Kato, K., J. Polymer Sci., B4, 35 (1966).

In the fluorinated PS-FPBD materials, the fluorine atoms attached to thePBD blocks use up the unsaturated sites, thus preventing staining ofthis block with OsO₄. The fluorine itself is not a heavy enough elementto enhance contrast in TEM. The PS block of the fluorinated samples canbe stained with RuO₄. Thus, stained fluorinated samples will haveopposite contrast to the original PS-PBD, i.e., dark stained PS blocksand light FPBD blocks. In the sulfonated and fluorinated PSS-FPBDmaterials, staining of the PSS block with RuO₄ is possible for a numberof reasons. In most cases, the PSS block will not be fully sulfonatedand thus unmodified PS monomers will be present to react with the stain.Additionally, the sulfonated PSS monomers might still retain theirreactivity with RuO₄. Finally, the TEM imaging contrast in the PSS-FPBDmaterials can be enhanced by exchanging the counter ion of the sulfonategroup, normally Na⁺, for a heavier cation such as Cs⁺. See Belloni. L.,et al., Chem, Phys., 119, 7560 (2003).

Small angle scattering experiments can be performed on all samples toaccurately determine the lattice symmetries and spacings of themorphologies. Small angle X-ray scattering (SAXS) and small angleneutron scattering (SANS) can be used to study model graft copolymers.SAXS can be performed, for example, by using a rotating anode source anda two-dimensional area detector. The use of a heavy counterion for thePSS blocks enhances contrast in SANS experiments, but is not necessaryto obtain good SANS results.

Further, many of the materials synthesized have deuterated PS blocks.This deuteration, produced by the use of fully deuterated d-PS monomerin the initial anion polymerization, is retained through postpolymerization fluorination and sulfonation treatments. Deuterationallows SANS to be used to compare the morphologies of the PS-PBD,PS-FPBD, and PSS-FPBD without interference from chemical treatments orstaining procedures.

Example 6 Vapor and Charge Transport Experiments

The investigation of the permeability of the materials to water vaporand methanol, as well as the efficiency of proton transport, isimportant for applications of the presently disclosed materials in fuelcells and in breathable barrier materials for chemical-biologicalprotection. High water vapor permeability enhances the utility of thematerials for breathable barrier applications, and the ability tohydrate the material also is necessary for the fuel cell membraneapplication. For fuel cell applications, it also is important that thematerials limit methanol transport.

Accordingly, the presently disclosed the fluorinated and sulfonatedblock copolymers can be characterized by using the same sorption balancedevice and the same morphological analysis of connectivity and transportpath tortuosity to investigate their water vapor and methanol transportproperties. In the presently disclosed subject matter, it is the PSSdomain connectivity that controls the properties. Of course, thesetransport properties also will be influenced by non-morphologicalchemical factors, such as degree of PS sulfonation. By developing dataof the type shown in FIGS. 8 and 10 for inert gases, for water vapor andmethanol, allows one to choose materials and morphologies to optimizematerials for the desired applications.

A major factor controlling vapor or charge transport in the materials isthe morphological connectivity of conductive sulfonated PS domainswithin the nonconductive fluorinated diene matrix. The effect ofmorphological connectivity on transport properties on model block andgraft copolymers of PS and polydiene has been previously reported. SeeLaverdure, K. S. In Chemical Engineering; University of Massachusetts:Amherst, Mass., 2001.

In this previous work, the permeability of non-interacting gases such asN₂, Ar, O₂, and CO₂ in PS-polydiene materials was studied. In thesematerials, at room temperature, the rubbery polydiene microdomains areas much as 100 times more permeable to these gases than the glassy PSdomains. Therefore, in morphologies, such as polydiene cylinders in a PSmatrix or lamellar structures, the sample spanning connectivity orpercolation paths in the polydiene domains control the transportbehavior. See Csernica. J., et al., Macromolecules, 20, 2468 (1987);Csernica, J., et al., Macromolecules, 22,1493 (1989); Rein. D. H., etal., Macromolecules, 23, 4456 (1990); Kinning. D. J., et al.,Macromolecules, 20,1129 (1987); Saxs. J. and Ottino. J. M., PolymerEngineering and Science, 23, 165 (1983); and Mohanty. K. K., et al.,Chemical Engineering Science, 37,905 (1982).

Transport studies were carried out using a sorption balance devicefollowing the basic design described previously. See Kinning. D. J., etal., Macromolecules, 20,1129 (1987); and Saxs. J. and Ottino. J. M.,Polymer Engineering and Science, 23, 165 (1983). By measuring massuptake with time, diffusion coefficients, solubilities, and thuspermeabilities can be obtained.

FIG. 8 provides experimental data from previous work showing the O₂permeability of PS-polyisoprene block copolymers as a function ofcomposition and morphology for lamellar and cylindrical samples both at0.50 polyisoprene volume fraction. All the morphologies are bounded bythe calculated envelope bounded by parallel law (upper) and series law(lower) transport. Additional studies focusing on lamellar morphologiesshowed transport dependences on morphological grain size and degree ofgrain orientation. See Laverdure. K. S. In Chemical Engineering;University of Massachusetts: Amherst, Mass., 2001.

FIGS. 9A and 9B show a schematic comparison of possible transportpathways in lamellar materials with small isotropic grains (FIG. 9A) andlarge anisotropic grains (FIG. 9B). It is known that the boundariesbetween adjacent grains in FIGS. 9A and 9B allow for connectivity ofconductive microdomains across the boundaries, and thus allow for readytransport from one grain into the next. See Gido, S. P., et al.,Macromolecules, 26, 4506 (1993); Gido, S. P. and Thomas. B. L.,Macromolecules, 27, 849 (1994); Gido. S. P. and Thomas. B. L.,Macromolecules, 27, 6137 (1994); Gido. S. P. and Thomas, B. L.,Macromolecules, 30, 3739 (1997); Burgaz. E. and Gido. S. P.,Macromolecules, 33, 8739-8745 (2000); Matsen. M. W., J. Chem. Phys.,107, 8110 (1997); Netz, R. R., et al., Physical Review Letters, 79, 1058(1997); and Villain-Guillot. S., et al., Physica A, 249, 285 (1998).

Clearly the tortuosity of transport paths is potentially larger insamples with large grains oriented in a direction perpendicular to thedirection of transport. Transport data from studies on the influence ofmorphology type as well as on grain size and degree of long range ordercan all be unified through the following result from percolation theoryfor the effective permeability, P_(eff), of a composite of a conductingmaterial and nonconducting obstacles: P_(eff)=(φ_(c)/T)P_(c); whereinφ_(c) and P_(c) are the volume fraction and permeability of theconductive microphase, respectively. The effective permeability isinversely proportional to the tortuosity, T, of transport paths in theconductive domains.

FIG. 10 shows all the permeability data for three gases obtained inprevious studies of both morphology type and grain size and orientation.Measured effective material permeability is plotted vs. φ_(c)/T whereφ_(c) is known from the polydiene volume fraction of the blockcopolymers and T is estimated from the TEM and SANS analysis ofmorphology, grain size, and degree of orientation. For the three gasesstudied, a linear relationship between permeability and φ_(c)/T isobserved, with the slope giving the permeability of the polydienedomains to the gas used.

Accordingly, the presently disclosed fluorinated and sulfonated blockcopolymers can be characterized by using the same sorption balancedevice and the same morphological analysis of connectivity and transportpath tortuosity to investigate their water vapor and methanol transportproperties. In the presently disclosed subject matter, it is the PSSdomain connectivity that controls the properties. Of course, thesetransport properties also are influenced by non-morphological chemicalfactors, such as degree of PS sulfonation.

Example 7 Mechanical Experiments

Previous work has related the molecular architecture, morphology, andmechanical properties of well-defined multigraft copolymers with thearchitectures shown in FIGS. 1A-1E: trifunctional combs, tetrafunctionalcentipedes, and hexafunctional barbwire. The general results of thesestudies are that, other things being equal (PS volume fraction andaverage number of grafts per molecule), increasing junction pointfunctionality increases material strength and elasticity. And for afixed PS volume fraction and junction point functionality, increasingthe number of junction points per molecule increases the strength,strain at break, and elasticity. The best materials from these previousstudies equaled the strength and exceeded the elasticity and strain atbreak performance of commercial thermoplastic elastomers, such asKRATON® and STYROFLEX® materials (BASF, Florham Park, N.J., UnitedStates of America). In the currently disclosed subject matter, the blockand graft copolymer materials are mechanically evaluated after they havebeen fluorinated and sulfonated. Applications of the fluorinated andsulfonated materials as barrier materials for chemical-biologicalprotection or as fuel cell membranes require good mechanical strengthand toughness, and in the case of fuel cells good mechanical propertiesat elevated temperatures of between about 100° C. and 150° C.

FIG. 11 shows a typical stress vs. strain curve based on previous datafor PS-Polydiene based materials. These tests utilize a scaled down ASTMstandard “dog bone” and obtain good testing statistics by reusing brokentensile specimens to produce new specimens for further testing. This isdone by redissolving the broken dog bones in solution, casting andannealing new sample films from which new dog bones are cut. As a resultof these procedures, each tensile test curve shown in FIG. 11 is thecomposite of 10 individual runs.

FIG. 12 shows the dependence on the number of branch points per moleculeof tensile strength for tetrafunctional centipede graft copolymers withpolydiene backbones and PS grafts obtained from previous data. Eachpoint on these curves results from the average of at least 10 individualtensile testing experiments. The PS volume fractions of these materialsare about 0.22, in the range targeted for the presently disclosed graftcopolymer cylinders. Increasing the number of junction points permolecule increases strength and also the elasticity in these highlyelastomeric materials. Once fluorinated and sulfonated, materials ofthis type likely will be less elastic, but likely will retain someflexibility, as well as their excellent strength and toughness whichresults, as illustrated in FIG. 13, from the microphase separation ofmultiple grafts into a number of different microphase separated domains.

FIG. 14 shows the increase in tensile strength and elasticity withincreasing graft point functionality 3, 4, and 6 obtained from previousdata. The materials compared in FIG. 14, have a relatively low number ofjunction points per molecule (about 4 in all cases) and thus theabsolute values of strength are not particularly impressive. The trend,however, of improving mechanical robustness with increasing graftfunctionality is evident.

In the mechanical properties evaluation of the presently disclosed graftcopolymer cylinders the strength and toughness of a range of materials(Table 1) with different graft functionalities and different numbers ofbranch points per molecule are compared. In addition to tensile tests atroom temperature, tensile performance at elevated temperatures, as in anoperating fuel cell, is evaluated. Also, dynamical mechanical, creep,and fatigue performance of these materials at room and elevatedtemperatures is evaluated. Also, thermogravimetric analysis (TGA) isused to investigate the chemical stability of the fluorinated andsulfonated materials at the elevated temperatures, up to 150° C.,envisioned for fuel cell applications. Other TGA studies investigate thestability of these materials up to higher temperatures where degradationwill likely occur. In all cases, TGA thermal stability analysis of thepresently disclosed PSS-FPBD materials are compared to controlexperiments run on NAFION® material.

It will be understood that various details of the presently disclosedsubject matter can be changed without departing from the scope of thepresently disclosed subject matter. Furthermore, the foregoingdescription is for the purpose of illustration only, and not for thepurpose of limitation.

1. A method for forming a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene, the method comprising: (a) providing an AB block copolymer, wherein the A block comprises a polystyrene component and the B block comprises a polydiene component; (b) reacting the polydiene component of the copolymer with a fluorinating agent to form a fluorinated polydiene component; and (c) reacting the polystyrene component of the copolymer with a sulfonating agent to form a sulfonated polystyrene component; thereby forming an AB block copolymer wherein the A block comprises a sulfonated polystyrene and the B block comprises a fluorinated polydiene.
 2. The method of claim 1, wherein the polydiene component is selected from the group consisting of 1,4-polybutadiene, poly(1,3-cyclohexadiene), and polyisoprene.
 3. The method of claim 1, wherein the fluorinating agent comprises difluorocarbene.
 4. The method of claim 1, wherein the polystyrene is selected from the group consisting of polystyrene and poly(α-methylstyrene).
 5. The method of claim 1, wherein the sulfonating agent is selected from the group consisting of acetyl sulfate and sulfur trioxide.
 6. A method for forming a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene, the method comprising: (a) providing an ABA triblock copolymer, wherein each of the A blocks of the triblock copolymer comprises a polydiene component and the B block of the triblock copolymer comprises a polystyrene component; (b) reacting the polydiene components of the copolymer with a fluorinating agent to form fluorinated polydiene components; and (c) reacting the polystyrene component of the copolymer with a sulfonating agent to form a sulfonated polystyrene component; thereby forming an ABA triblock copolymer wherein each of the A blocks comprises a fluorinated polydiene and the B block comprises a sulfonated polystyrene.
 7. A method for forming a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene, the method comprising: (a) providing a graft copolymer comprising a polydiene backbone and a plurality of grafted polystyrene side chains; (b) reacting the polydiene backbone of the graft copolymer with a fluorinating agent to form a fluorinated polydiene backbone; and (c) reacting the polystyrene side chains of the graft copolymer with a sulfonating agent to form sulfonated polystyrene side chains; thereby forming an graft copolymer comprising a fluorinated polydiene and a sulfonated polystyrene.
 8. The method of claim 7, wherein the graft copolymer comprises an architecture, wherein the architecture is selected from the group selected from a trifunctional comb architecture, a tetrafunctional centipede architecture, a hexafunctional branch point architecture, and a miktoarm star architecture.
 9. A copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 1. 10. A proton exchange membrane comprising a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 1. 11. An electrochemical cell comprising the proton exchange membrane of claim
 10. 12. A polyelectrolyte comprising a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 1. 13. A fabric comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 1. 14. An article of chemical-biological protective clothing comprising the fabric of claim
 13. 15. An article of material for protecting an agricultural product comprising the fabric of claim
 13. 16. A template for sol-gel polymerization comprising a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 1. 17. The method of claim 6, wherein the polystyrene is selected from the group consisting of polystyrene and poly(α-methylstyrene).
 18. A copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 6. 19. A proton exchange membrane comprising a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 6. 20. An electrochemical cell comprising the proton exchange membrane of claim
 19. 21. A polyelectrolyte comprising a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 6. 22. A fabric comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 6. 23. An article comprising the fabric of claim 22, wherein the article comprises one of chemical-biological protective clothing or material for protecting an agricultural product.
 24. A template for sol-gel polymerization comprising a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 6. 25. The method of claim 7, wherein the polystyrene is selected from the group consisting of polystyrene and poly(α-methylstyrene).
 26. A copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 7. 27. A proton exchange membrane comprising a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 7. 28. An electrochemical cell comprising the proton exchange membrane of claim
 27. 29. A polyelectrolyte comprising a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 7. 30. A fabric comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 7. 31. An article comprising the fabric of claim 30, wherein the article comprises one of chemical-biological protective clothing or material for protecting an agricultural product.
 32. A template for sol-gel polymerization comprising a copolymer comprising a fluorinated polydiene and a sulfonated polystyrene formed by the method of claim
 7. 